Porous inorganic oxide materials prepared by non-ionic surfactant templating route

ABSTRACT

A method for the preparation of new semi-crystalline, porous inorganic oxide compositions possessing uniform framework-confined mesopores in the range 2.0-10.0 nm. The method uses an interaction between various nonionic polyethylene oxide based surfactants (N°) and neutral inorganic oxide precursors (I.sup.□) at ambient reaction temperatures. The materials formed exhibit a disordered assembly of worm-like channels of regular diameter owing to the specific mechanism of self-assembly, producing highly stable materials and particles incorporating large numbers of the channels. This (N° I°) templating approach introduces several new concepts to mesostructure synthesis. The application of the low-cost, non-toxic and biodegradable surfactants and ambient reaction temperatures, introduces environmentally clean synthetic techniques to the formation of mesostructures. Recovery of the template can be achieved through solvent extraction where the solvent may be water or ethanol.

GOVERNMENT RIGHTS

The present invention was sponsored under National Science FoundationContract CHE 9224102. The Government has certain rights to thisinvention.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.08/465,770, filed Jun. 6, 1995 U.S. Pat. No. 5,622,684.

BACKGROUND OF INVENTION

(1). Field of Invention

This invention relates to the synthesis of crystalline, porous inorganicoxide materials possessing a disordered assembly of worm-like channels.In particular, the present invention relates to such materials where theformation of the mesoporous structure is accomplished by a novelself-assembly mechanism involving complexation and/or hydrogen (H)bonding between aqueous or alcoholic emulsions of various nonionicpolyethylene oxide based surfactants (N°) and various neutral inorganicoxide precursors (I°). This is followed by hydrolysis and subsequentcondensation of hydrolysis products at ambient reaction temperatures.This (N°I°) templating approach allows for the removal of templatethrough calcination or solvent extraction which lowers material andenergy costs. The template is biodegradable. The (N°I°) templatingapproach also affords non-lamellar mesostructures of metal oxides inaddition to silica.

(2). Description of Prior Art

Modern human activities rely greatly upon porous solids of both naturaland synthetic design. The pore structures of such solids are generallyformed during crystallization or during subsequent treatments. Thesesolid materials are classified depending upon their predominant poresizes: (i) microporous, with pore sizes <1.0 nm; (ii) macroporous, withpore sizes exceeding 50.0 nm; and mesoporous, with pore sizesintermediate between 1.0 and 50.0 nm. Macroporous solids find limiteduse as adsorbents or catalysts owing to their low surface areas andlarge non-uniform pores. Micro- and mesoporous solids however, arewidely utilized in adsorption, separation technologies and catalysis.There is an ever increasing demand for new, highly stable well definedmesoporous materials because of the need for ever higher accessiblesurface areas and pore volumes in order that various chemical processesmay be made more efficient or indeed, accomplished at all.

Porous materials may be structurally amorphous, para-crystalline orcrystalline. Amorphous materials, such as silica gel or alumina gel, donot possess long range crystallographic order, whereas para-crystallinesolids such as γ- or η- alumina are semi-ordered, producing broad X-raydiffraction peaks. Both these classes of materials exhibit very broadpore distributions predominantly in the mesoporous range. This wide poredistribution however, limits the effectiveness of catalysts, adsorbentsand ion-exchange systems prepared from such materials.

Zeolites and some related molecular sieves such as; alumino-phosphatesand pillar interlayered clays, possess rigorous uniform pore sizes.Zeolites are highly crystalline microporous aluminosilicates where thelattice of the material is composed of IO₄ tetrahedra (I=Al, Si) linkedby sharing the apical oxygen atoms. Cavities and connecting channels ofuniform size form the pore structures which are confined within thespecially oriented IO₄ tetrahedra (Breck, D. W., Zeolite MolecularSieves: Structure, Chemistry and Use; Wiley and Sons; London, pages 1 to100 (1974)). Zeolites are considered as a subclass of molecular sievesowing to their ability to discriminate small molecules and performchemistry upon them. Molecular sieves in general are materials withcrystalline frameworks in which tetrahedral Si and/or Al atoms of azeolite or zeolitic lattice are entirely or in part substituted by otheratoms such as B, Ga, Ge, Ti, Zr, V, Fe or P. Negative charge is createdin the zeolite framework by the isomorphous substitution of Si⁴⁺ ions byAl ³⁺ or similar ions. In natural zeolites, this charge is balanced bythe incorporation of exchangeable alkali or alkaline earth cations suchas Na⁺, K⁺, Ca²⁺. Synthetic zeolites utilize these and other cationssuch as quaternary ammonium cations and protons as charge balancingions. Zeolites and molecular sieves are generally prepared fromaluminosilicate or phosphate gels under hydrothermal reactionconditions. Their crystallization, according to the hereafter discussedprior art, is accomplished through prolonged reaction in an autoclavefor 1-50 days and oftentimes, in the presence of structure directingagents (templates). The correct selection of template is of paramountimportance to the preparation of a desired framework and pore network. Awide variety of organic molecules or assemblies of organic moleculeswith one or more functional groups are known in the prior art to providemore than 85 different molecular sieve framework structures. (Meier etal., Atlas of Zeolite Structure types, Butterworth, London, pages 451 to469 (1992)).

Recent reviews on the use of templates and the corresponding structuresproduced, as well as the mechanisms of structure direction have beenproduced by Barrer et al., Zeolites, Vol. 1, 130-140, (1981); Lok et al., Zeolites, Vol. 3, 282-291, (1983); Davis et al., Chem Mater., Vol. 4,756-768, (1992) and Gies et al., Zeolites, Vol 12, 42-49, (1992). Forexample, U.S. Pat. No. 3,702,886 teaches that an aluminosilicate gel(with high Si/Al ratio) crystallized in the presence of quaternarytetrapropyl ammonium hydroxide template to produce zeolite ZSM-5. Otherpublications teach the use of different organic templating agents andinclude; U.S. Pat. No. 3,709,979, wherein quaternary cations such astetrabutyl ammonium or tetrabutyl phosphonium ions crystallize ZSM-11and U.S. Pat. No. 4,391,785 demonstrates the preparation of ZSM-12 inthe presence of tetraethyl ammonium cations. Other prior art teachesthat primary amines such as propylamine and i-propylamine (U.S. Pat. No.4,151,189), and diamines such as diaminopentane, diaminohexane anddiaminododecane (U.S. Pat. No. 4,108,881) also direct the synthesis ofZSM-5 type structure. Hearmon et al (Zeolites, Vol. 10, 608-611, (1990))however, point out that the protonated form of the template molecule ismost likely responsible for the framework assembly.

In summary, most of the zeolites and molecular sieve frameworks taughtin the prior art are assembled by using quaternary ammonium cations orprotonated forms of amines and diamines as templates.

The need for new and useful types of stable frameworks and the need toexpand the uniform pore size into the mesopore region allowing theadsorption and discrimination of much larger molecules, has driven thesearch for organic structure-directing agents that will produce thesenew structures. In the prior art however, molecular sieves possessuniform pore sizes in the microporous range. These pore sizes andtherefore the molecular sieving abilities of the materials arepredetermined by the thermodynamically favored formation of frameworkwindows containing 8, 10 and 12 I-atom rings. The largest pore sizezeolites previously available were the naturally occurring faujasite(pore size 0.74 nm) or synthetic faujasite analogs, zeolites X and Ywith 0.8 nm pore windows (Breck, D. W., Zeolite Molecular Sieves:Structure, Chemistry and Use; Wiley and Sons; London, pages 1 to 100(1974)). The innovative use of aluminophosphate gels has allowed thesynthesis of new large pore materials. Thus, an 18 I-atom ringaluminophosphate molecular sieve; VPI-5 (Davis et al., Nature, Vol. 331,698-699, (1988)) was produced and found to consist of an hexagonalarrangement of one dimensional channels (pores) of diameter ≈1.2 nm. Agallophosphate molecular sieve cloverite, with pore size of 1.3 nm wasreported by Estermann M. et al (Nature, Vol 352, 320-323, (1991)), whilerecently, Thomas J. M. et al (J. Chem. Soc. Chem. Commun., 875-876,(1992)) reported a triethyl ammonium cation directed synthesis of anovel 20 I-atom ring aluminophosphate molecular sieve (JDF-20), withuniform pore size of 1.45 nm (calculated from lattice parameters). Avanadium phosphate material was very recently reported with 1.84 nmlattice cavity (Soghmonian et al., Agnew. Chem. mnt. Ed. Engl., Vol. 32,610-611, (1993)). However, the true pore sizes of the latter twomaterials are unknown since sorption data were not made available andfurthermore, these materials are not thermally stable.

In summary, in spite of significant progress made toward the preparationof large pore size materials, thermally stable molecular sieves arestill only available with uniform pore sizes in the microporous range.

A recent breakthrough in the preparation of mesoporous silica andaluminosilicate molecular sieves was disclosed in U.S. Pat. Nos.5,098,684; 5,102,643. The class of mesoporous materials (denoted asM41S) claimed in this prior art was found to possess uniform andadjustable pore size in the range 1.3-10.0 nm. These materials exhibitedframework wall thickness from 0.8 to 1.2 nm and elementary particle sizegenerally greater than 50.0 nm. By varying the synthesis conditions,M41S materials with hexagonal (MCM-41), cubic (MCM-48) or layeredmorphologies have been disclosed (Beck et al., J. Am. Chem. Soc., Vol.114, 10834-10843, (1992)). The mechanism proposed for the formation ofthese materials involves strong electrostatic interactions and ionpairing between long chain quaternary alkyl ammonium cations, asstructure directing agents, and anionic silicate oligomer species (U.S.Pat. No. 5,098,684). Recently, Stucky et al (Nature, Vol. 368, 317-321(1994)) extended this assembly approach by proposing four complementarysynthesis pathways. The direct co-condensation of anionic inorganicspecies (I⁻) with a cationic surfactant (S⁺) to give assembled ion pairs(S+ I⁻), for example MCM-41, was described as Pathway 1. The chargereversed situation with an anionic template (S⁻) being used to directthe assembly of cationic inorganic species (I⁺) to ion pairs (S⁻, I⁺)was Pathway 2. Hexagonal iron and lead oxide and lamellar lead andaluminum oxide phases have been reported using Pathway 2 (Stucky et al.ibid.). Pathways 3 and 4 involve the mediation of assemblies ofsurfactants and inorganic species of similar charge by oppositelycharged counterions (X⁻ =Cl⁻, Br⁻, or M⁺ =Na⁺, K⁺). The viability ofPathway 3 was demonstrated by the synthesis of hexagonal MCM-41 using aquaternary alkyl ammonium cation template under strongly acidicconditions (5-10 mol L⁻¹ HCl or HBr) in order to generate and assemblepositively charged framework precursors (Stucky et al. ibid). Pathway 4was demonstrated by the condensation of anionic aluminate species withan anionic template (C₁₂ H₂₅ OPO₃ ⁻) via alkali cation mediated (Na⁺,K⁺) ion pairing, to produce a lamellar Al(OH)₃ phase. Pinnavaia et al.(Nature, Vol 368, 321-323, (1994)) reported the preparation of atemplated mesoporous silica and a Ti-substituted analogue by the acidcatalyzed hydrolysis of an inorganic alkoxide precursor in the presenceof primary ammonium ions.

All of the aforementioned synthetic pathways involve charge matchingbetween ionic organic directing agents and ionic inorganic precursors.The template therefore, is strongly bound to the charged framework anddifficult to recover. For example, in the original Mobil patent (U.S.Pat. No. 5,098,684) the template was not recovered, but burned off bycalcination at elevated temperature. Template removal of anionicsurfactant (Pathway 2) has however, been demonstrated by ion-exchangewith low pH acidic cation donor solutions (U.S. Pat. No. 5,143,879).Template-halide pairs in the framework of acidic Pathway 3 materials canbe displaced by ethanol extraction (Stucky et al. ibid). Thus, ionictemplate recovery is possible, provided that exchange ions or ion pairsare present during the extraction process.

Most recently, the formation of mesoporous molecular sieves via a newroute (Pathway 5) was proposed by Pinnavaia et al. (Science, Vol. 267,865-867, (1995)). In this method, the self assembly of micelles ofneutral primary amines (S°) and neutral inorganic alkoxide precursors(I°) was based upon hydrogen bonding between the two components. The newapproach (S°, I°) taught in that prior art afforded mesostructures withgreater wall thicknesses, smaller particle sizes and complimentaryframework-confined mesoporosities relative to Pathway 1 and 3 materials.The new materials however, provided several advantages over thematerials taught in the prior art. Greater wall thicknesses are desiredin order that the thermal and hydrothermal stabilities of the materialsmay be improved (Coustel et al., J. Chem. Soc. Chem. Commun., 967-968,(1994)). Small particle sizes allow for greater volumes of texturalmesoporosity in turn leading to greater access, via mass transportthrough the textural pores, to the framework-confined pores, therebyimproving the overall performance of the adsorbent (Pinnavaia et al.,ibid; Chavin et al., J. Catal., Vol. 111, 94-105, (1988)). In addition,owing to the weak template-framework interactions, Pathway 5 allowed forthe facile solvent extraction of the template, removing the need forcation donors or ion pairs.

The terms framework-confined and textural porosity are herein defined.Framework-confined uniform pores are pores formed by the nucleation andcrystallization of the framework elementary particles and are typicallyhighly regular cavities and channels confined by the solid framework.The size of these cavities and channels is predetermined by thethermodynamically favored assembly routes. Textural porosity is thatwhich can be attributed to voids and channels between elementaryparticles and/or aggregates of such particles (grains). Each elementaryparticle in the case of molecular sieves is composed of a certain numberof framework unit cells each in turn containing framework-confineduniform pores. Textural porosity is formed during crystal growth andsegregation or during subsequent thermal treatment or acid leaching. Thesize of the textural pores is determined by the size, shape and thenumber of interfacial contacts of these particles or aggregates. Thus,the size of the textural pores is generally one or two orders ofmagnitude larger than that of the framework-confined pores and isproportional to the elementary particle size.

One skilled in the arts of powder X-ray diffraction (XRD), ScanningElectron Microscopy (SEM), Transmission Electron Microscopy (TEM) andadsorption/desorption can determine the existence of and differentiatebetween framework-confined and textural mesoporosities. Thecrystallographic distance between repeat units in the elementaryparticles and some information about the arrangement of such repeatunits can be obtained from XRD. Particle sizes and shapes andpreliminary information regarding textural mesoporosity can beestablished by SEM and TEM. Analysis of the N₂ or Aradsorption-desorption isotherms of the solid material can indicate bothframework-confined and textural mesoporosities. Textural mesoporosity isevidenced by the presence of a Type IV isotherm exhibiting a welldefined hysteresis loop in the relative pressure region P_(i) /P₀ >0.5(Sing et al. , Pure Appl. Chem., Vol. 57, 603-619, (1985)). Thisbehavior is common for a variety of para-crystalline materials andfreeze-dried pillared layered solids. Framework-confined mesoporosity ischaracterized by a sharp adsorption uptake followed by a step loop inthe 0.2-0.7 P_(i) /P₀ region. This step corresponds to filling of theframework-confined mesopores. In MCM-41 materials, the large particlesize precludes the formation of textural mesoporosity and acorresponding ratio of textural to framework-confined mesoporosityapproaching zero is calculated. In materials prepared via Pathway 5, theelementary particle size was smaller (<40.0 nm) producing a ratio oftextural to framework-confined mesoporosity greater than 0.2.

In summary, according to the prior art, the molecular sieve materialsand preparation techniques provide several distinct disadvantages andadvantages:

i) The prior art of Pathways 1 through 4 teaches the use of chargedsurfactant species as templates in order to assemble inorganicframeworks from charged inorganic precursors. These charged templatesare generally expensive, strongly bound to the inorganic framework andtherefore difficult to recover. Additionally, many of these templatessuch as the most commonly used quaternary ammonium cations are highlytoxic and environmentally undesirable. In the prior art of Pathways 1 to4, the template was removed from the structure by either calcining itout or by ion-exchange reactions. Pathway 5 prior art templates are alsohighly toxic and environmentally unsuitable, but may be removed throughenvironmentally benign ethanol extraction and thereby recovered andreused.

ii) Prior art mesoporous molecular sieves produced by Pathways 1-4exhibit small pore-wall thicknesses (0.8-1.2 nm), to which may berelated the very poor thermal and hydrolytic stabilities of thematerials taught in that prior art, while Pathway 5 provides materialswith greater wall thicknesses (2.0 nm) and thereby greater stabilities.This contrast is ascribed to the differences in the self-assemblymechanisms with the former prior art relying on strong ionicinteractions and the latter relying on weaker H-bonding interactions.

iii) The prior art of Pathways 1-4 produces materials with low texturalto framework-confined mesopore ratios, while the prior art of pathway 5exhibits higher textural to framework-confined mesopore ratios andtherefore, theoretically better access to the framework pores. However,the very small elementary particle size means that few pores arecontained within any one particle, thereby theoretically producing lowerspecific activities.

There is a need for new methods of preparation of new materials of thesetypes, cost reductions, ease of recoverability and environmentalcompatibility in the template and inorganic precursors has lead to thedevelopment of a new synthetic method to be described herein.

OBJECTS OF THE INVENTION

It is therefore an object of the present invention to provide a newapproach to the design and synthesis of crystalline inorganic oxidecompositions with a disordered assembly of worm-like channels. Further,it is an object of the present invention to provide inexpensivetemplates, precursors and methods while avoiding high energy demandingand costly hydrothermal syntheses. Further, it is an object of thepresent invention to provide a template system that allows for facilerecovery and thereby recycling of the template from the condensedinorganic structure via solvent extraction. Further, it is an object ofthe present invention to provide a template system that affordsinorganic oxide compositions through lower cost, lower toxicity thaneither quaternary ammonium or amine surfactants and templatebiodegradability. Finally, it is an object of the present invention toprovide for the preparation of well defined non-layered mesoporousstructures of oxide materials derived from metals other than silicon,that are not accessible through the prior art. These and other objectswill become increasingly apparent by reference to the followingdescription and the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are graphs showing representative X-ray powderdiffraction patterns of MCM-41 (FIG. 1A) Beck et al., J. Am. Chem. Soc.,Vol. 114, 10834-10843, (1992) and HMS (FIG. 1B) Pinnavaia et al.(Science, Vol. 267, 865-867, (1995) products.

FIGS. 2A and 2B are graphs showing representative N₂adsorption-desorption isotherm for MCM-41 (FIG. 2A) Beck et al., J. Am.Chem. Soc., Vol. 114, 10834-10843, (1992) and HMS (FIG. 2B) Pinnavaia etal. (Science, Vol. 267, 865-867, (1995) products.

FIG. 3 is a graph showing the X-ray powder diffraction patterns of theas synthesized (curve A) and calcined (curve B) MSU-1 products fromExample 3.

FIG. 4 is a graph of the N₂ adsorption-desorption isotherm for thecalcined MSU-1 product from Example 3. FIG. 4A is a graph of thecorresponding Horvath-Kawazoe framework-confined mesopore sizedistribution curve.

FIG. 5 is a graph of the X-ray powder diffraction patterns of the assynthesized (curve A) and calcined (curve B) MSU-3 products from Example16.

FIG. 6 is a graph of the N₂ adsorption-desorption isotherm for thecalcined MSU-3 product from Example 16. FIG. 6A is a graph of thecorresponding Horvath-Kawazoe framework-confined mesopore sizedistribution curve.

FIG. 7 is a graph of the X-ray powder diffraction patterns of theas-synthesized (curve A) and calcined (curve B) MSU-3 Alumina productsof Example 19.

FIG. 8 is a graph of the N₂ adsorption-desorption isotherm for thecalcined MSU-3 Alumina product from Example 19. FIG. 8A is a graph ofthe corresponding Horvath-Kawazoe framework-confined mesopore sizedistribution curve.

FIG. 9 is a representative chemical structure of a secondary fattyalcohol poly-ethoxylate (Tergitol™).

FIG. 10A is a representative chemical structure of an alkyl phenolpoly-ethoxylate (TRIton X™). FIG. 10B is Igepal RC-760.

FIG. 11 is a representative chemical structure of a fatty acidethoxylate.

FIG. 12 is a representative chemical structure of an ethyleneoxide-propylene oxide-ethylene oxide tri-block co-polymer (PLURONIC64L™).

FIG. 13 is a representative chemical structure of the ethylene diaminepropylene oxide-ethylene oxide derivative (TETRONIC™).

FIG. 14 is a representative chemical structure of a primary fatty aminepoly-ethoxylate.

FIG. 15 is a representative chemical structure of a fatty acid PPO/PEOblock co-polymer.

FIG. 16 is a representative chemical structure of a sorbitan ethoxylate.

FIG. 17 shows powder X-ray diffraction patterns of MSU-3 aluminatemplated by Pluronic 64L surfactant: A! as-synthesized sample after airdrying at room temperature for 16 hr; B! after calcination at 873° K inair for 6 h.

FIG. 18 shows a transmission electron micrograph of MSU-1 aluminatemplated by Tergitol 15-S-9 surfactant and calcined at 773° K in air. Aworm-like motif of regular mesopores of approximately 3.0 nm in diameteris observed.

FIG. 19a shows a nitrogen adsorption and desorption isotherms for MSU-3alumina templated by Pluronic 64L and calcined at 773° K in air for 4 h.The volume of N₂ sorbed is expressed at standard temperature andpressure; P/P₀ is the partial pressure of nitrogen in equilibrium withthe sample at 77° K. FIG. 19B shows CorrespondingBarrett-Joiner-Halender pore size distribution determined from the N₂adsorption isotherm; dW/dR is the derivative of the normalized N₂ volumeadsorbed with respect to the diameter of the adsorbent. Prior toanalysis, the samples were evacuated at 423° K, 10⁻⁶ torr for 16 hours.

FIG. 20 shows a ²⁷ Al MAS NMR spectra of MSU-3 alumina templated byPluronic 64L surfactant: A as-synthesized sample after air drying atroom temperature for 16 hours; B after calcination at 773° K in air for4 hours. The chemical shifts are referenced to external Al H₂ O!₆ ³⁺.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to a synthetic, semi-crystalline inorganicoxide composition having at least one resolved x-ray reflectioncorresponding to a lattice spacing of 3 to 10 nm, framework confinedchannels between about 2 and 10 nm diameter, and a specific surface areaof 300 to 1400 square meters per gram and having a disordered assemblyof worm-like channels.

The present invention also relates to a method for the preparation of asynthetic semi-crystalline inorganic oxide composition which comprises:providing a mixture of (i) a neutral inorganic oxide precursor (I°)containing at least one element selected from the group consisting ofdi-, tri-, tetra-, penta- and hexavalent elements and mixture thereof;(ii) a non-ionic poly(alkylene oxide) surfactant (S°) as a template; and(iii) a hydrolyzing agent; mixing the solution to form a gelcontainingthe composition; separating at least some of the hydrolyzing agent andthe surfactant to form the composition; and optionally calcining thecomposition wherein the composition has a disordered assembly ofworm-like channels.

The present invention further relates to a method for the preparation ofa synthetic, semi-crystalline inorganic oxide composition whichcomprises: preparing a solution of a neutral inorganic oxide precursor(I°), containing at least one element selected from the group consistingof di-, tri-, tetra-, penta- and hexavalent elements and mixturesthereof with stirring and optionally aging the inorganic oxide precursor(I°) solution; preparing a homogeneous solution of a nonionicpoly(alkylene oxide) surfactant (S°) as a template in a hydrolyzingagent, and optionally in a co-solvent, by stirring it at a temperaturebetween about minus 200° and plus 100° C.; mixing of the solutions ofsteps (a) and (b) at a temperature between about minus 20° and plus 100°C. to form a gel which is aged for at least about 30 minutes to form thecomposition; separating at least some of the hydrolyzing agent andsurfactant from the composition; and optionally calcining thecomposition, wherein the composition has a disordered assembly ofworm-like channels.

The present invention further relates to a method for the preparation ofa crystalline inorganic oxide composition which comprises: preparing ahomogeneous solution of nonionic poly(ethylene oxide) surfactant as atemplate (N°) in a lower alkyl alcohol solvent by mixing at ambienttemperature; adding an inorganic metal precursor to the solution of step(a) at ambient temperature under stirring for at least 30 minutes toform a homogeneous solution; slowly adding a solution of a hydrolyzingagent to the homogeneous solution to form a gel as a first precipitatein the aqueous solution; aging of the first precipitate with stirring;redispersion of the first precipitate in a lower alkyl alcohol; agingthe redispersion under stirring at ambient temperature for 16 to 48hours to form a second precipitate; separating the aqueous solution,lower alkanol and at least some of the template from the secondprecipitate by washing once with ethanol; drying the second precipitatein air at ambient temperature to form the composition; optionally heattreating the second precipitate to at least 373° K in air for at least16 hours; optionally removing the template by solvent extraction; andoptionally calcining the second precipitate to remove any remaining ofthe template and to cross-link the framework at between about 673° K and973° K in air for at least 4 hours, wherein the composition has adisordered assembly of worm-like channels.

The present invention further relates to a method for the preparation ofsynthetic, semi-crystalline inorganic silicon dioxide composition whichcomprises: preparing a homogeneous aqueous solution of a nonionicpoly(ethylene oxide) derived surfactant template (N°) with mixing atambient temperature; adding an inorganic silica precursor to thesolution of step (a) at ambient temperature with stirring to form asolid, precipitate; aging of the precipitate with stirring at ambienttemperature for between 16 and 48 hours; separating the aqueous solutionand template from the precipitate followed by washing once withdeionized water; drying the precipitated and separated precipitate inair at ambient temperature; heat treating the air dried precipitate inair at least 373 ° K for at least 16 hours; optionally removing anyremaining template by solvent extraction from the heat treatedprecipitate; and calcining the precipitate to remove any remainingtemplate to cross-link the framework at between 673° K and 973° K in airfor at least 4 hours to form the composition, wherein the compositionhas a disordered assembly of worm-like channels.

The present invention provides to a new route to the synthesis ofsemi-crystalline materials with a disordered assembly of worm-likechannels. The compositions produced in the current invention aredistinguished from those of the prior art by the virtue of the method ofpreparation of the present invention, the subsequent architecture of themesoporous structure and the range of templated metal oxides other thansilica that is afforded by this route. Formation of the mesoporousnetwork is accomplished by interaction (complexation and/orhydrogen-bonding) between a nonionic polyethylene oxide based surfactanttemplate and neutral inorganic precursors, followed by hydrolysis andsubsequent condensation of the inorganic reaction product under eitherambient or elevated temperature reaction conditions and the subsequentremoval of the solvent phase and the template.

The present invention particularly provides a preferred totally nonionic(N° I°) route to the preparation of quasi-crystalline oxide compositionscomprising (a) preparing a homogeneous solution or emulsion of anonionic polyethylene oxide-based surfactant (N°) by stirring,sonicating or shaking at standard temperature and pressure (STP); (b)addition of one or more neutral inorganic precursors with stirring atstandard temperatures and pressures (STP) to the emulsion of step (a) atambient temperature to form a precipitated semi-crystalline product; (c)separating the solvent and the hydrolyzing agent from the precipitatedproduct by filtration or centrifugation; (d) optionally calcining thequasi-crystalline product at 673° K to 873° K for at least 4 hours inair or (e) extracting the template through solvent extraction wherebythe solvent is either water or ethanol.

The present invention thus provides a new route to inorganic oxidecrystalline materials with a disordered assembly of worm-like channelsthat can be utilized as adsorbents, catalysts and catalyst supports forthe catalytic conversion of organic substrates. The present invention isdistinguished from the prior art by the new preparative N° I° methodused to obtain the mesoporous crystalline inorganic oxide materials, thepore morphology of the said materials and the range of templatedmesoporous metal oxide materials that may be prepared by this method.According to the method of the present invention, the formation of themesoporous structure is accomplished by interaction (complexation and/orhydrogen bonding) between template molecules within micellar aggregatesof nonionic polyethylene oxide-based templates and neutral inorganicoxide precursors, followed by hydrolysis and cross linking of IO_(x)units, where I is a central metallic or non-metallic element coordinatedto x oxygen atoms (2≦x≦6). This interaction is most likely to occurbetween an I-OH unit and the terminal OH function of each surfactantmolecule, or between the I-OH unit and the array of lone pair electronson the template polar segment. The polar segment of the template in thepresent invention is flexible and appears to act in the fashion of acrown ether complexing a I-OH unit, thereby stabilizing a site ofnucleation for subsequent condensation of the mesoporousquasi-crystalline inorganic oxide product, although the inventors do notwant to be bound to any particular theory.

The inventors know of no prior art teaching the preparation of micro-,meso-, or macro-porous inorganic oxide compositions by such a nonionicN° I° mechanism involving crystallization of inorganic oxide precursorsaround well defined micelles of nonionic surfactants. Specifically, thepresent result is achieved by using micelles of a nonionic surfactant totemplate and assemble a neutral inorganic reactant precursor into amesoporous framework structure. Complexation and/or hydrogen bondingbetween the template and the reagent is believed to be the primarydriving force of the assembly of the framework in the current invention.The aforementioned method consists of the formation of a solidprecipitate by the mixing of a solution or emulsion of a polyethyleneoxide-based nonionic surfactant, with a neutral inorganic oxideprecursor. The latter being an inorganic alkoxide, in the presence of ahydrolyzing agent, followed by aging and crystallization under stirring,sonication or shaking at ambient temperature for at least 16 h. Thetemplate may be recovered by extraction with ambient temperature alcoholor hot water whose temperature exceeds the cloud point of the template.Complete removal of the remainder of the template and final crosslinkingof the IO_(X) framework is accomplished by calcination in air attemperatures between 673° K and 973° K for at least 4 h.

The molar ratio of inorganic oxide precursor to surfactant is preferablybetween 10:1 and 20:1 depending upon the specific template being used.The concentration of surfactant in solution is between 0.003 mol L-¹ and0.4 mol L-¹ again depending upon the surfactant being used and the poresize desired.

The crystalline inorganic oxide composition of the present invention inits calcined state has the formula:

    nR-EO/A.sub.v G.sub.w C.sub.x D.sub.y O.sub.z

wherein A_(v) G_(w) C_(x) D_(y) O_(z) is written in anhydrous form,wherein R-EO is at least one of a selection of nonionic alkyl, oralkyl/aryl polyethylene oxide or polyethylene oxide-polypropyleneoxide-polyethylene oxide block co-polymer molecules wherein when R-EO ispresent n is between about 0.01 and 1; A is at least one optionaltrivalent element selected from the group consisting of B, Cr, Al, Gaand Fe; G is at least one optional tetravalent metallic element selectedfrom the group consisting of Ge, Ti, V, Hf and Zr; Si is silicon; D isan optional and is a pentavalent or hexavalent element selection fromthe group consisting of Sb, Cr, Nb, Ta, V, W and Mo; O is oxygen and v,w, X, y and z are the molar stoichiometries of A, G, Si, D and Orespectively, wherein in the composition when calcined, n is about 0,0.0015≦V≦2, 0.001≦W≦1, 0.001≦X≦1, 0.001≦Y≦2 and 1≦Z≦3.

The comosition can have the formula nR-EO/A_(X) O_(Y), wherein A_(x)O_(y) is written in anyhydrous form, wherein R-EO is selected from thegroup consisting of nonionic alkyl polyethylene oxide, alkyl and arylpolyethylene oxide, and polyethylene oxide-polypropyleneoxide-polyethylene oxide block co-polymer molecules; and wherein whenR-EO is present, n is between about 0.01 and 1; A is a metal atom; O isoxygen and x and y are the molar stoichiometries of A and O, such thatin the composition when calcined, n is about O, x is about 1 and y isbetween about 1 and 3.

The semi-crystalline mesoporous materials of the present invention maybe described as being formed by hydrogen-bonding between the terminalhydroxyl function or the array of lone pair electrons on the O atoms ofthe ethylene oxide units of the template molecules and any M-(OR)_(x)compound. This H-bonding is followed by hydrolysis and subsequentcondensation and cross-linking of IO_(x) units under ambient or elevatedtemperature reaction conditions. Specifically, the said method comprisesthe formation of an organic/inorganic solution by the mixing of anaqueous or alcoholic solution of nonionic surfactant with the desiredamount of Si-alkoxide, M-Si double alkoxide, mixtures of Si-andM-alkoxides or pure M-alkoxides (where M=Al, Ca, Cr, Fe, Ga, Ge, Mg, Mo,Nb, Sb, Sn, Ti, V, W, or Zr), followed by aging and subsequentprecipitation under stirring for at least 16 h.

The composition of this invention is characterized by at least onestrong XRD peak at a basal spacing (d₁₀₀) of at least 3.0 nm or larger.(The designation d₁₀₀ is arbitrary and not intended to imply any longrange hexagonal, cubic or lamellar order for the compositions.) Thecompositions are also distinguished in part from those of the prior art,specifically MCM-41 materials, by the assembly of worm-like channels.

In the present invention, the template may be removed from the condensedreaction products in at least three different ways: (i) air dryingfollowed by calcination in air or in inert gas preferably at atemperature from 673° K to 973° K for 4 to 6 h; (ii) solvent extractionof the template from the air dried material using alcohol or hot water;(iii) combination of (i) and (ii).

Procedure (i) results in the complete oxidation and therebydecomposition of the occluded template. The current invention improveson the environmental impact of the prior material preparation art, asthe oxidation products of quaternary ammonium and amine based surfactanttemplates described in the prior art, include environmentallyundesirable NO_(x) gases, while the oxidation products of polyethyleneoxide based surfactants are the more environmentally compatible H₂ O andCO₂ gasses. Procedure (ii) allows the template to be recovered andsubsequently recycled and reused. If the template is removed byprocedure (ii), the product should be calcined in air or inert gas toremove the final traces of the template and to complete the crosslinking of the mesostructure.

After calcination, the present compositions may be used as adsorbents,molecular sieves, catalysts and catalyst supports. When the calcinedproduct is appropriately substituted or subsequently impregnated astaught in Ger. Pat. (DD) No. 286,522, with the correct amount of acatalytically active element, such as Al, Rh, Nb, Re, Ag, Cu, Cr, Pt,Pd, Ti, V, Zr or mixtures thereof, or when intercalated with transitionmetal inorganic metallocycles, it can be used as a catalyst forcracking, hydrocracking, hydrogenation-dehydrogenation, isomerization oroxidations involving large and small organic substrates.

The new synthesis method of the compositions of this invention involvesthe preparation of solutions or emulsions of a surfactant templatecompound and reaction of this solution with liquid di-, tri-, tetra-,penta- or hexa-valent metal or metalloid hydrolyzable reagents in thepresence of a hydrolysing agent under stirring, sonication or shaking,until formation of the desired precipitated product is achieved andrecovering the solid material. The template is described moreparticularly as a nonionic (neutral) polyethylene oxide based moleculethat would possess one of many different molecular structures and thehydrolysing agent is described as water.

There are four basic types of surfactant molecules that are describedherein. The alkyl-polyethylene oxides; such as are related to theTERGITOL 15-S-m products (FIG. 9) are derived from the reaction ofethylene oxide with a primary or secondary alcohol and possess the basicformula R_(n) --O(EO)_(m) H where R is a hydrophobic alkyl group with nranging from 1 to at least 20 carbon atoms, EO is a hydrophilic ethyleneoxide unit (OCH₂ CH₂) with m ranging from about 7 to 40, preferably atleast 20.

The alkyl-phenyl polyethylene oxides; such as IGEPAL-RC (FIG. 10B) andTRITON-X (FIG. 10A), possess the same range of structures as thealkyl-polyethylene oxides, with the exception that the primary (IGEPALRC), secondary or tertiary (TRITON X) R group is bound to the EO unitsthrough a hydrophobic phenoxy group (PhO). These molecules then, havethe basic formula; R_(n) --Ph--O(EO)_(m) H, preferably where m is 8 to10 and n is 8.

The polyethylene oxide (PEO)-polypropylene oxide (PPO) molecules; suchas PLURONIC (FIG. 12), are derived from the addition of hydrophobicpropylene oxide to propylene glycol followed by the addition ofhydrophilic ethylene oxide. They are defined as PEO_(n) -PPO_(m)-PEO_(n) tri-block co-polymers wherein n is controlled by length toconstitute from 10% to 80% by weight of the final product. The order ofthe PEO and PPO units may be reversed in order to produce the PPO_(m)-PEO_(n) -PPO_(m) triblock co-polymers; PLURONIC-R. Preferably n is 30and m is 13.

A fourth basic PEO based surfactant type is derived by from thesubstitution of the hydrogens of ethylene diamine by ethylene oxide andpropylene oxide units to form the X shaped, TETRONIC, molecules (FIG.13) with basic formula; ((EO)_(n) -(PO)_(m))₂ --NCH₂ CH₂ N-((PO)_(m)-(EO)_(n))₂. The order of the PEO and PPO groups in these molecules mayalso be reversed to form TETRONIC-R. Preferably m is 13 and n is 30.

The preferred preparation procedures of the said compositions comprisesteps as follows:

(i) preparing a solution of the desired template under stirring, in asolvent that is either, water for the preparation of silicon dioxide, oralcohol for the preparation of metal oxide compositions from morereactive alkoxide precursors;

(ii) addition of the desired metal oxide precursor to the surfactantsolution under stirring, sonication or shaking;

(iii) preparation of a solution of the hydrolysing agent in the alcoholused in step (i). The hydrolysing agent is water;

(iv) very slow addition of the hydrolysing agent to thetemplate/inorganic precursor solution under stirring. (iii and iv arenot required if templated silica is being prepared);

(v) aging of the total solution for at least 16 h up to 48 h at roomtemperature;

(vi) separation of the product from the supernatant liquid by filtrationor centrifugation;

(vii) air drying of the product followed by heat treatment at 373° K;

(viii) separation of the template by extraction with either ethanol orhot water or a mixture thereof; and

(ix) calcination of the templated product in air or inert gas at between473° K and 973° K for 0.5 h for extracted compositions or for 4 to 6 hfor unextracted products.

The inorganic oxide precursors are single or double metal alkoxidecompounds, The list of preferred alkoxides includes but not exclusively:aluminum(III) ethoxide, aluminum(III) isopropoxide, aluminum(III) n-,sec- or tert- butoxide, antimony(III) isopropoxide, antimony(III)n-butoxide, calcium(II) ethoxide, calcium(II) isopropoxide, calcium(II)tert- butoxide, chromium(IV) isopropoxide, chromium(IV) tert- butoxide,copper(II) methoxyethoxide, gallium(III) isopropoxide, germanium(IV)ethoxide, germanium(IV) isopropoxide, indium(III) isopropoxide,iron(III) ethoxide, iron(III) isopropoxide, iron(III) tert- butoxide,lead(II) isopropoxide, lead(II) tert- butoxide, magnesium(II) ethoxide,manganese (II) isopropoxide, molybdenum(V) isopropoxide, niobium(V)ethoxide, silicon(IV) methoxide, silicon(IV) ethoxide, silicon(IV)propoxide, silicon(IV) butoxide, silicon(IV) hexoxide, strontium(II)ethoxide, tin(IV) isopropoxide, titanium(IV) ethoxide, titanium(IV)propoxide, titanium(IV) isopropoxide, titanium(IV) butoxide,titanium(IV) octadecoxide, tungsten(VI) ethoxide, tungsten (VI)isopropoxide, vanadium(V) triisopropoxide oxide, zinc(II) isopropoxide,zinc(II) tert- butoxide, zirconium(IV) n- propoxide, zirconium(IV)isopropoxide, zirconium(IV) butoxide, zirconium(IV) tert- butoxide,aluminum(III) silicon(IV) alkoxide, titanium(IV) silicon(IV)polyethoxide and other mixtures of the aforementioned alkoxidecompounds. The alcohols used in step (i) of the preparation artcorrespond to the alcoholate ligand from which the metal alkoxide isderived. The alcohols thus preferred are methanol, ethanol, n- andisopropanol and n-, sec-, tert-, butanol. The alcohols contain 1 to 4carbon atoms.

Said mixed metal alkoxides are obtained through proprietary preparationsor by reaction of desired metal alkoxides in desired molar ratios underreflux (433° K) for 3-4 h.

The said reacting of the inorganic precursor and the template solutionis achieved at room temperature (298° K to 303° K) under stirring for atleast 16 h.

Aging of the reaction mixture may be achieved at room temperature eitherunder stirring, sonication or shaking or by being left to stand for atleast 24 h. More specifically, the reacting occurs through complexationor H-bonding between a neutral nonionic template and neutral inorganicoxide precursors, followed by hydrolysis and crosslinking of IO_(X)units at ambient or elevated reaction temperatures. The complexation, orH-bonding most likely occurs between the terminal OH group of thetemplate molecules and the hydrolyzable ligand on the inorganicprecursor molecule, or between the inorganic precursor molecule and theelectron lone pairs of the ethylene oxide groups in the hydrophilic headgroup of the template molecules.

The calcination is performed in a temperature controlled oven by heatingin air at a rate of 2° K min⁻¹ to a final temperature between 673° K and973° K for at least 30 min, preferably 4 to 6 h.

The outstanding features of the present invention are:

(i) The use of nonionic (N°) polyethylene oxide based templates, toassemble mesoporous metal oxide framework compositions with a worm-likearray of channels of regular diameter in the mesopore size range;

(ii) The use of neutral metal alkoxide inorganic oxide precursors (I°);

(iii) The reaction of solutions of inorganic oxide precursors underreflux for 3-4 h in order to obtain polymerized I-O-I' species;

(iv) The use of hydrogen bonding or non-electrostatic complexation asthe driving force for the neutral N° I° assembly of the nonionictemplate and the neutral inorganic oxide precursor species;

(v) The use of ambient reaction conditions to prepare the templatedproduct;

(vi) The recovery and recycling of the template through simple solventextraction from the product.

(vii) The use of low cost, non-toxic, biodegradable and low energyrequirement preparation art.

The templated inorganic oxide compositions of the present invention canbe combined with other components, for example, zeolites, clays,inorganic oxides or organic polymers or mixtures thereof. In this wayadsorbents, ion-exchangers, catalysts, catalyst supports or compositematerials with a wide variety of properties may be prepared.Additionally, one skilled in the art may impregnate or encapsulatetransition metal macrocyclic molecules such as porphyrins orphthalocyanines containing a wide variety of catalytically active metalcenters.

Additionally, the surfaces of the compositions can be functionalized inorder to produce catalytic, hydrophilic or hydrophobic surfaces. Thisfunctionalization can be introduced during the synthesis procedure byreplacing the metal alkoxide precursor with alkyl metal alkoxideMR(OR)_(X-1) ! reactants, or metal carboxylate reactants. The surfacesmay be functionalized after synthesis by reaction with variouschlorides, fluorides, sylisation or alkylating reagents.

The following are specific examples of the present invention intended toillustrate but not to limit the invention.

EXAMPLES 1-6

The desired amount of one of a range of TERGITOL 15-S templates, withvarying hydrophilic head group lengths, was dissolved in one hundredmilliliters of deionized H₂ O under stirring at room temperature, untila homogeneous solution was obtained. The appropriate quantity of Si(OC₂H₅)₄ was added at once to the above template solution under stirring atroom temperature. The reaction stoichiometry expressed in terms of molesper mole Si correspond to the following:

0.1 mol R_(n) --(OCH₂ CH₂)_(m) OH

50 mol H₂ O

The resulting solution was stirred and aged for 16 h at roomtemperature. During the initial 1-3 h stirring, white templated productswere observed as solid precipitates. The products were separated fromthe mother liquor through filtration or centrifugation and dried at roomtemperature. The template was then removed through calcination in air at973° K for 4 h.

The X-ray powder diffraction (XRD) patterns of all the samples wereobtained with a RIGAKU ROTAFLEX (Japan) diffractometer equipped with arotating anode and CU_(Ka) radiation (l=0.15148 nm). The diffractiondata were recorded by step scanning at 0.02 degrees of 2 theta, wheretheta is the Bragg angle and photon counting time of 1 sec step⁻¹. Thed-spacings of the X-ray reflections of the samples were calculated innm. Transmission electron micrographs were obtained on a JEOL JEM 100CXII (Japan) electron microscope by observing unmodified particlessupported on carbon coated copper grids (400 mesh). The sample imageswere obtained using an accelerating voltage of 120 kV, a beam diameterof approximately 5 mm and an objective lens aperture of 20 mm. The porestructures of said compositions were characterized by measuring N₂adsorption-desorption isotherms using a Coulter 360CX (Florida)sorptometer. Isotherms were recorded at 70° K using a standardcontinuous sorption procedure. Before measurement, each sample wasoutgassed overnight at 323° K and 10⁻⁶ Torr. The specific surface area(S_(BET), m² g⁻¹) and the total pore volumes (V_(t), mL g⁻¹), which wereconsistent with mesoporous structures, were calculated from theadsorption isotherms following IUPAC recommendations (Sing et al., PureAppl. Chem., 57, 603-619 (1985)). The pore size distributions of thecompositions were calculated following the method of Horvath and Kawazoe(G. Horvath and K. J. Kawazoe, J. Chem. Eng. Jpn., 16, 470-475 (1983)).Thermogravimetric analyses of the samples were performed under a flow ofdry N₂ gas on a CAHN system thermogravimetric gas (TG) analyzer using aheating rate of 5° K min⁻¹. The amounts of each surfactant used in theexamples 1-6, together with the corresponding physico-chemicalparameters are summarized in Table 1.

                  TABLE 1                                                         ______________________________________                                                         Amount                                                                        of                      BET                                                   template        HK pore Surface                                      Template used.      d.sub.100                                                                          diameter                                                                              area                                 Example formula  (g)        (nm) (nm)    (m.sup.2 g.sup.-1                    ______________________________________                                        1       Tergitol 5.15       4.4  2.2     900                                          15-S-7                                                                2       Tergitol 5.84       5.2  2.5     1010                                         15-S-9                                                                3       Tergitol 7.38       4.1  3.1     1005                                         15-S-15                                                               4       Tergitol 8.77       5.4  2.6     640                                          15-S-15                                                               5       Tergitol 10.79      7.8  4.8     605                                          15-S-20                                                               6       Tergitol 15.58      7.9  4.5     525                                          15-S-30                                                               ______________________________________                                         *The Material designation is MSU1.                                       

EXAMPLES 7-11

In Examples 7 to 9 the concentration of the template in aqueous solutionwas varied in order to modify the effective channel size distribution.This teaching is not apparent in synthetic strategies of the prior art(U.S. Pat. Nos. 5,098,684, 5,102,643 and 5,057,296).

To 100 milliliters of deionized water was added 1%, 5%, 10% 15% and 25%by weight of surfactant per weight of solvent under stirring at roomtemperature. To these solutions was added the appropriate amount ofSi(OC₂ H₅)₄ so that the Si:surfactant molar ratio was 10:1. The relativereaction stoichiometry with respect to Si and surfactant remainedconstant for each example, while the reaction stoichiometry of water permole of Si changed with each preparation. The reaction stoichiometriescorresponded to the following:

    ______________________________________                                        Example 7:         Example 8:                                                 0.1 mol R.sub.n --(OCH.sub.2 CH.sub.2).sub.15 OH                                                 0.1 mol R.sub.n --(OCH.sub.2 CH.sub.2).sub.15 OH           492 mol H.sub.2 O. 98 mol H.sub.2 O.                                          Example 9:         Example 10:                                                0.1 mol R.sub.n --(OCH.sub.2 CH.sub.2).sub.15 OH                                                 0.1 mol R.sub.n --(OCH.sub.2 CH.sub.2).sub.15 OH           33 mol H.sub.2 O.  29 mol H.sub.2 O.                                          Example 11.                                                                   0.1 mol R.sub.n --(OCH.sub.2 CH.sub.2).sub.15 OH                              20 mol H.sub.2 O.                                                             ______________________________________                                    

The resulting precipitate was aged under stirring at room temperaturefor 16 h to obtain the templated product. The product was thentransferred into sealed containers and heated at 373° K for a further 16h. The crystalline product was then filtered, dried at room temperatureand calcined at 973° K for 4 h to remove the occluded template. Thephysico-chemical properties of the calcined templated products aredescribed in Table 2.

                  TABLE 2                                                         ______________________________________                                                         Amount                                                                        of                      BET                                                   template        HK pore Surface                                      Template used       d.sub.100                                                                          diameter                                                                              area                                 Example formula  (g)        (nm) (nm)    (m.sup.2 g.sup.-1)                   ______________________________________                                        7       Tergitol 1.0        4.3  2.0     655                                          15-S-15                                                               8       Tergitol 5.0        3.6  2.0     465                                          15-S-15                                                               9       Tergitol 10.0       3.9  2.0     515                                          15-S-15                                                               10      Tergitol 15.0       4.0  2.2     890                                          15-S-15                                                               11      Tergitol 25.0       5.5  2.5     700                                          15-S-15                                                               ______________________________________                                         *The Material designation is MSU1.                                       

EXAMPLES 12 and 13

The following examples were prepared to confirm the ability ofalkyl-phenyl polyethylene oxide surfactants to act as templating agentsfor mesostructure formation in the manner of the present invention.

Aqueous solutions of TRITON-X 100 and TRITON-X (FIG. 10A) 114 wereprepared as in the manner of the preparation art of Examples 1 through11. The concentration of template was 7.50% weight of surfactant perweight of solvent. Si(OC₂ H₅)₄ was added at once in the appropriateamount so that the Si:surfactant molar ratio was 10:1 as in thepreparation art of Examples 1 through 11. The remainder of the synthesiswas identical to the preparation art described in Examples 1 through 6.The calcined templated products exhibited XRD patterns, BET surfaceareas, HK pore size distributions and pore wall thicknesses as describedin Table 3.

                  TABLE 3                                                         ______________________________________                                                          Amount                                                                        of                     BET                                                    template       HK pore Surface                                      Template  used.     d.sub.100                                                                          diameter                                                                              area                                 Example formula   (g)       (nm) (nm)    (m.sup.2 g.sup.-1)                   ______________________________________                                        12      C.sub.8 Ph(EO).sub.8                                                                    2.3       6.1  2.0     780                                  13      C.sub.8 Ph(EO).sub.10                                                                   2.7       6.2  3.5     715                                  ______________________________________                                         *The Material designation is MSU2.                                       

EXAMPLES 14-16

Examples of the present preparation art are presented for compositionsprepared by templating with various concentrations of the nonionicsurfactant PLURONIC 64L. This surfactant differs from those discussed inthe prior examples in that the hydrophobic part of the surfactantmolecule is based on propylene oxide units. The molecule is defined as apolyethylene oxide-polypropylene oxide- polyethylene oxide tri-blockco-polymer.

Aqueous solutions of PLURONIC 64L (FIG. 12) with concentrations of 50%,10% and 15% weight of surfactant per weight of solvent were prepared asin the preparation art of the previous examples 1 through 13. Si(OC₂H₅)₄ was added at once in the appropriate amount so that theSi:surfactant molar ratio was 20:1. The remainder of the preparation wasidentical to the preparation art of examples 7 through 11. The calcinedtemplated products exhibited physico-chemical properties as described inTable 4.

                  TABLE 4                                                         ______________________________________                                                         Amount                                                                        of                      BET                                                   template        HK pore Surface                                      Template used.      d.sub.100                                                                          diameter                                                                              area                                 Example formula  (g)        (nm) (nm)    (m.sup.2 g.sup.-1)                   ______________________________________                                        14      (PEO).sub.13-                                                                          5.0        7.5  8.5     1090                                         (PPO).sub.30-                                                                 (PEO).sub.13                                                          15      (PEO).sub.13-                                                                          10.0       7.1  6.7     1150                                         (PPO).sub.30-                                                                 (PEO).sub.13                                                          16      (PEO).sub.13-                                                                          15.0       6.1  5.8     1190                                         (PPO).sub.30-                                                                 (PEO).sub.13                                                          ______________________________________                                         *The Material designation is MSU3.                                       

EXAMPLE 17

Example 17 demonstrates the viability of recovering the template fromthe inorganic structure prior to calcination through solvent extraction.

A 0.05 g quantity of the air dried and heat treated at 373° K butnon-calcined product of Example 14 is examined by thermogravimetricanalysis (TGA) under N₂ gas flow at a heating rate of 5° K C min⁻¹. Onegram of the same air dried and non-calcined product of Example 14 isstirred in 100 milliliters of hot water (≈363° K) for 3 h. The productis then filtered and washed with a second and a third 100 millilitervolumes of hot water. The filtered product is then dried at roomtemperature for 16 h. This product is then analyzed by TGA andvibrational spectroscopy.

EXAMPLES 18 and 19

This example demonstrates the ability of the present invention toprepare compositions whereby framework Si atoms have been substituted bydifferent metal atoms, for example Ti.

A substituted or polymerized metal alkoxide compound is formed byreaction of Si(OC₂ H₅)₄ with Ti(OCH(CH₃)₂)₄ such that the molar % of Tifor each composition was 0.5%, 1.0% and 5.0%. The appropriate amount ofTi(OCH(CH₃)₂)₄ is dissolved in the appropriate quantity of Si(OC₂ H₅)₄under stirring. The resultant solution is then heated under reflux atthe boiling point of the Si(OC₂ H₅)₄ (433° K ) for 4 h. The solution isthen cooled to room temperature and added to a solution of nonionicpolyethylene oxide based surfactant in the appropriate ratio as taughtin Examples 1 through 16. The preparation art then follows that ofExamples 7 through 11. The physico-chemical properties of Zr- andTi-substituted MSU-1 compositions are presented in Table 5.

                  TABLE 5                                                         ______________________________________                                                                                   BET                                                                           Surface                            Material         Template  %    d.sub.100                                                                           HK   area                               designation                                                                           Example  formula   Metal                                                                              (nm)  (nm) (m.sup.2 g.sup.-1                  ______________________________________                                        Zr-MSU-1                                                                              18       C.sub.11-15 (EO).sub.12                                                                 5    4.9   3.0  950                                Ti-MSU-1                                                                              19       C.sub.11-15 (EO).sub.12                                                                 5    4.9   2.8  940                                ______________________________________                                    

EXAMPLES 20-23

This example describes the preparation art of nonionic surfactanttemplated mesoporous aluminum oxide.

The desired amount of PLURONIC 64L was dissolved under stirring at roomtemperature in 50 milliliters of an alcohol corresponding to thealkoxide ligand of the aluminum alkoxide inorganic precursor, which inthe present art, was sec-butanol. The appropriate amount ofAl(OCH(CH₃)CH₂ CH₃)₃ was then dissolved in that solution such that theAl: surfactant molar ratio was 10:1. No precipitation reaction wasobserved at this point. An aliquot of deionized H₂ O was dissolved in 10milliliters of sec-butanol such that the H₂ O:Al molar ratio was 2:1.This solution was added very slowly to the Al/surfactant solution understirring at room temperature. Gel and precipitate formation wereobserved at this point. The solution was stirred for 4 h after whichanother 25 milliliters of sec-butanol was added to disperse the gel. Theresultant composition was stirred until homogeneous then left to standfor 16 h. The product was filtered, washed once with ethanol, dried inair at room temperature, heat treated at 373° K for 16 h then calcinedin air at 773° K.

The physico-chemical properties of Examples 20-24 are presented in Table6.

                  TABLE 6                                                         ______________________________________                                                                Amount      HK     BET                                                        of          pore   Surface                            Material      Template  template                                                                             d.sub.100                                                                          diameter                                                                             area                               designation                                                                           Ex.   formula   used.(g)                                                                             (nm) (nm)   (m.sup.2 g.sup.-1)                 ______________________________________                                        MSU-3   20    (PEO).sub.13-                                                                           8.6    6.3  4.2    420                                Alumina       (PPO).sub.30-                                                                 (PEO).sub.13                                                    MSU-1   21    C.sub.11-15 (EO).sub.9                                                                  15     8.0  5.8    488                                Alumina                                                                               22    C.sub.11-15 (EO).sub.12                                                                 14     n.o. 6.8    425                                        23    C.sub.11-15 (EO).sub.20                                                                 14     n.o. 7.2    530                                MSU-4   24    C.sub.18 Ph(EO).sub.18                                                                  14     n.o. 8.0    420                                Alumina                                                                       ______________________________________                                         N.O. = Not observed in range 1-20° 2 theta.                       

EXAMPLES 24, 25, 26, 27

Mesoporous alumina molecular sieves, designated MSU-1, -2 and -3aluminas, were prepared by the ambient temperature hydrolysis ofaluminum tri-sec-butoxide using different types of nonionicpolyethylene-oxide surfactants as the structure directing agents.

The synthesis of a representative product, MSU-3 alumina, prepared usinga polyethylene oxide (PEO)--polypropylene oxide (PPO) co-polymersurfactant illustrates the general procedure for the preparation of amesoporous alumina molecular sieve. The specific template employed wasPLURONIC 64L (BASF Corp.), a tri-block co-polymer with specificstoichiometry (PEO)₁₃ -(PPO)₃₀ (PEO)₁₃. A solution containing 42 mmolesof the de-ionized water in 10 mL of anhydrous sec-butanol was then addedvery slowly (˜1 mL min⁻¹) to a stirred homogeneous solution containing2.1 mmoles of surfactant and 21 mmoles of aluminum tri-sec-butoxide in25 mL of anhydrous sec-butanol. The overall reaction stoichiometry was,therefore, 0.1:1.0:2.0 surfactant:Al:water. After the addition of thewater solution, the resulting gel was diluted in an equal volume ofsec-butanol and allowed to age under stirring for 3 hours, during whichtime the white particles were observed to grow larger. The product wasthen further aged at room temperature without stirring for an additional16 hours. The grainy, gelatinous product that separated from the solventwas filtered and washed with absolute ethanol to remove excess template,unreacted Al-alkoxide and solvent. The white powder was dried at roomtemperature for 16 hours and then at 373° K for 6 hours to encouragefurther condensation of the inorganic framework. Any remaining templatewas then removed by calcination in air at 773° K for 4 hours (heatingrate, 2° K min⁻¹).

X-ray diffraction patterns were obtained with a Rigaku Rotaflexdiffractometer equipped with a rotating anode and Cu-K.sub.α radiation(λ=0.15418 nm). The TEM image was obtained with a JEOL 100CX microscopeusing an accelerating voltage of 120 kV and a 20 μm objective lensaperture. N₂ isotherms were obtained on a Coulter Omnisorp 360CXSorptometer operated under continuous adsorption conditions. Frameworkconfined mesopore sizes were determined by Barrett-Joiner-Halender (BJH)analysis of the N₂ desorption isotherm and Horvath-K awazoe analysis ofthe adsorption isotherm. Surface areas were determined by the BETmethod. ²⁷ Al MAS NMR spectra were obtained using a Varian VXR-400 NMRspectrometer equipped with a Varian MAS probe and SiN rotor. Thespectrometer frequency was 104.22 MHz pulse width 2 ms, and samplespinning rate 6550 Hz.

The powder X-ray diffraction (XRD) patterns shown in FIG. 17 for theas-synthesized and calcined forms of MSU-3 alumina prepared from apolyethylene oxide-polypropylene oxide co-polymer surfactant of the type(PEO)₁₃ (PPO)₃₀ (PEO)₁₃ contained moderately broad reflections atapproximately 6.8 nm. The d₁₀₀ reflection for the calcined form wassubstantially more intense, but only slightly shifted to lower spacing,relative to the as-synthesized material. Similar single peak patternsalso have been observed for disordered hexagonal MCM-41 (Chen, C-Y., etal., Microporous Materials 2, 17 (1993); and Hou, Q., et al., Chem.Mater. 6, 1176 (1994)) mesostructures prepared by electrostatictemplating and for neutrally templated HMS (Tanev, P. T., et al.,Science 267, 865 (1995)) and MSU-X silicas. The widths of the d₁₀₀reflections of MSU-X aluminas were broader than those observed forhexagonally disordered MCM-41 materials, but similar to those of theMSU-X silicas. This XRD line broadening most likely is a result of alower degree of structural order and a broader pore size distributionthan observed for MCM-41 mesostructures.

Increases in the XRD intensities of mesostructured materials uponcalcination are not restricted to the MSU-X families of materials.Similar observations have been preported for MCM-41 and HMS silicas.Modeling studies have shown that the removal of the occluded organictemplate from hexagonal mesostructures enhances the Bragg scatteringcross-section. The decrease in the d₁₀₀ spacing (˜0.2 nm) is attributedto a contraction of the inorganic framework upon the removal of theorganic template. Several alumina mesostructures prepared from othernonionic templates (see below) exhibited d₁₀₀ reflections greater than9.0 nm.

PEO--based surfactants adopt spherical to long "worm-like" micellarstructures in aqueous solution (Porter, M. R., Handbook of Surfactants2nd ed, Blackie Academic & Professional, London (1994); Chu, B.,Langmuir 11,414 (1995); and Lin, Z., et al., Langmuir, 8, 2200 (1992)).The pore structures of MSU-X aluminas prepared from these NO templatesreflect the novel worm-like motif of the assembled surfactant. Theworm-like channels, though more or less regular in diameter, have nodesirable range order. That is the packing channel system appears to berandom, despite the presence of an XRD reflection. Clearly thedisordered channel system of the MSU-X aluminas is in marked contrast tothe long range hexagonal arrangement of channels formed for MCM-41 andHMS mesostructures (C. T. Kresge, et al., Nature 359:710 (1992); and P.T. Tanev, et al., Science, 267:865 (1995)). Evidence for thisunprecedented mesopore structure was obtained from transmission electronmicrograph (TEM) images of MSU-1 alumina prepared from the alkylated PEOsurfactant TERGITOL 15-S-9 (Union Carbide). As shown by the micrographin FIG. 18, the alumina particles indeed are penetrated by a worm-likemotif of channels of regular diameter.

FIG. 19 provides a representative N₂ adsorption/desorption isotherm fora MSU-3 alumina calcined at 773° K. All of the MSU-X aluminas preparedby PEO surfactant templating display a similar, broad, but well defined,step in the adsorption isotherm at P/P_(O) ≈0.45-0.8 and a hysteresisloop in the desorption isotherm over the same relative pressure range.These features result from the condensation of the adsorbate within theframework-confined mesopores (Branton, P. J., et al., J. Chem. Soc.Faraday Trans. 90, 2965 (1994)) and not from interparticle pores (Gregg,S. J., et al., Adsorption, Surface Area and Porosity, 2nd ed., AcademicPress London (1982)). The lack of textural mesoporosity is indicatedfurther by the absence of a hysteresis loop above P/P_(O) =0.8 (Tanev,P. T., et al., Science 267, 865 (1995)). Some `necking` or `blocking` ofthe pore structure, perhaps caused by the intersection or overlapping ofthe worm-like surfactant micelles, is suggested by the sharp curvaturein the desorption leg of the framework-confined hysteresis loop.

Most previously reported studies of mesoporous molecular sieves havemade use of the Horvath-K awazoe (HK) model (Horvath, G., et al., J.Chem. Eng. Jpn. 16,470 (1983)) for the determination of pore sizedistributions from N₂ adsorption isotherms. This model, developed formicroporous lamellar carbons, assumes slit-like micropores. Therefore,its applicability to materials with larger, cylindrical mesopores islikely to be limited. In this report, we have applied in addition to theHK model both the Cranston-Inkley (CI) (Cranston, R. W., et al.,Advances in Catalysis, 9,143 (1970)) and the Barrett-Joyner-Halender(BJH) (Barrett, E P., et al., J. Amer. Chem. Soc. 73,373 (1951)) modelsto the determination of framework pore size. Directly comparable poresize values were obtained when the CI and BJH models were applied to theN₂ adsorption and desorption branches, respectively. However,significantly larger pore diameters were obtained from fitting theadsorption data in the HK model. For instance, as shown in FIG. 19B, theBJH pore-size distribution for MSU-3C alumina calcined at 773° K iscentered at 2.4 nm, whereas the HK model affords a value of 4.8 nm.Measurement of the pores observed in the TEM micrograph of MSU-1 aluminatemplated by TERGITOL 15-S-9 (FIG. 18) produced values of about 2.6 nm.This compares well to the corresponding BJH value of 3.3 nm.

Table 7 provides the basal spacings, surface areas, pore volumes, andthe HK and BJH pore sizes for MSU-X aluminas prepared from differentfamilies of PEO-based surfactants.

                  TABLE 7                                                         ______________________________________                                        Physico-chemical properties of MSU-X mesoporous                               alumina molecular sieves after calcination in air at                          773K.                                                                                                                     HK.sup.b                          Material                  Amount of                                                                            Surface    Pore                              designa-        Surfactant                                                                              Template                                                                             area  d.sub.100                                                                          size                              tion   Template formulae   mmol!.sup.a                                                                          m.sup.2 g.sup.-1 !                                                                  nm!  nm!                              ______________________________________                                        MSU-1  #Tergitol                                                                              C.sub.11-15  EO!.sub.9                                                                  10.7   490   8.0  5.5                               aluminas                                                                             15-S-9                                                                        Tergitol C.sub.11-15  EO!.sub.12                                                                 8.5    425   8.5  6.5                                      15-S-12                                                                       Tergitol C.sub.11-15  EO!.sub.20                                                                 5.8    535   9.0  7.0                                      15-S-20                                                                MSU-2  *Igepal  C.sub.12 Ph EO!.sub.18                                                                  5.9    420   9.6  8.0                               aluminas                                                                             RC-760                                                                        †Triton                                                                         C.sub.8 Ph EO!.sub.8                                                                    9.0    460   >9.0 8.0                                      X-114                                                                         Triton   C.sub.8 Ph EO!.sub.10                                                                   11.2   445   >9.0 8.0                                      X-100                                                                  MSU-3  ‡Pluronic                                                                    PEO!.sub.13-                                                                           2.1    430   6.8  4.0                               alumina                                                                              64L       PPO!.sub.30-                                                                  PEO!.sub.13                                                  ______________________________________                                         .sup.a All syntheses were performed at a surfactant concentration of 25 w     %.                                                                            .sup.b Mesopore volume for pores between 2.0 and 8.0 nm diameter of the       BJH analyses.                                                                 #Tergitol 15S-x surfactants kindly supplied by Union Carbide Corp. (Unite     States)                                                                       *Igepal RC760 kindly supplied by RhonePoulenc Co. (France)                    †TritonX surfactants supplied by Aldrich Co.                           ‡Pluronic 64L kindly supplied by BASF Co. (Detroit, MI)       

A mesostructure templating effect is indicated by the increase in boththe d₁₀₀ reflections and pore diameters with increasing size of thesurfactant molecule. Since the MSU-X aluminas exhibit similar pore sizesbut larger crystallographic repeat distances than those of MSU-Xsilicas, (Bagshaw, S. A., et al., Science, 269,1242 (1995)) we concludethat the pore wall thicknesses of the aluminas are substantially greaterthan those of the silica analogs. This is consistent with theobservation that the Brunauer-Emmett-Teller (BET) (Gregg, S. J., et al.,Adsorption, Surface Area and Porosity, 2nd ed., Academic Press, London(1982)) surface areas of the aluminas calcined in air at 773° K rangefrom 420 to 535 m² g⁻¹, whereas MSU-X silicas give values twice aslarge. Nevertheless, the surface areas and pore volumes for our MSU-Xaluminas are substantially higher than those of commonly availableamorphous and crystalline forms of alumina (Poisson, R., et al., incatalyst Supports and Supported Catalysts, (Ed: A. B. Stiles),Butterworths, Boston, p. 11 (1987)) prepared by traditional sol-gel orflash-calcination techniques (Gates, B. C., in Materials Chemistry: AnEmerging Discipline, American Chemical Society, Washington, D.C., p. 301(1995)).

The nature of the coordination environment of aluminum in MSU-X aluminaswas examined using ²⁷ Al MAS NMR spectroscopy. Spectra of as-synthesizedand calcined MSU-3 alumina (FIG. 20) display three resonances,uncorrected for quadrupolar shift, at δ=0, 35 and 75 ppm. These chemicalshifts are indicative of the existence of aluminum in three differentoxygen coordination environments (Akitt, J. W., Prog Nucl. Magn. Reson.Spectroasc. 21, 127 (1989); and Cruickshank, M. C., et al., J. Chem.Soc. Chem. Commun. 23 (1986)). The resonances at δ=35 and 75 areassigned to six-coordinated (Al_(oct)) and four-sites coordinated(Al_(tet)) centers, respectively, while the sites giving rise to theresonance at δ=35 are assigned to Al atoms in a five-fold coordinationgeometry (Al_(pent)) (Akitt, J. W., Prog. Nucl. Magn. Reson.Spectroasc., 21, 127 (1989); and Cruickshank, M. C., et al., J. Chem.Soc. Chem. Commun. 23 (1986)).

In the as-synthesized material the dominant species is Al_(oct) with theresonances due to Al_(tet) and Al_(pent) showing weaker intensities.After calcination at 773° K, however, the intensities of both theAl_(tet) and the Al_(pent) signals increase at the expense of theal_(oct) signal. In the as-synthesized form, coordination of surface Alatoms to the surfactant may be observed as Al_(oct). After removal ofthe surfactant, these Al atoms may adopt Al_(pent) environments. Anotherpossibility is defect site formation during the calcination procedure,wherein Al atoms in 6-fold coordination within the inorganic frameworkare transformed into lower coordination geometries upon dehydroxylation.

Porous aluminas (Adkins, H., et al., J. Amer. Chem. Soc. 73, 2184(1951); and Basmadjian, D., et al., J. Catal. 1, 547 (1962)) andaluminates (Sned, R., Appl. Catal. 12, 347 (1984)) have been preparedpreviously from alkoxide precursors in the presence of organic poreregulating agents such as methyl cellulose or short chain quaternaryammonium cations. Although these organic modifiers exhibited structuredirecting properties for zeolite syntheses (Introduction to ZeoliteScience and Practice, (Eds: H. van Bekkum, E. M. Flanigen, J. C. Jansen)Elsevier, Amsterdam (1991)), they afforded aluminas that were X-rayamorphous. Consequently, these earlier alumina synthesis reactionsinvolved modifier encapsulation, but not templating processes. Aluminaaerogels with surface areas near 500 m² g⁻¹ also have been reported(Chen, C-M., et al., Studi. Surf. Sci. Catal. 91, 427 (1995)), but thepore structures of these low bulk density materials were purelytextural. In contrast, the N°I° templating reactions of the presentinvention provide low cost, environmentally benign, ambient temperatureroutes to aluminas with a novel, random worm-like pore motif. Because oftheir unprecedented pore structure, thermal stability, high surface areaand multiple aluminum coordination environments, these novelmesostructures offer promising opportunities for new materialsapplications, particularly in chemical catalysis and molecularseparations.

Although aluminas are widely used as industrial catalysts and catalystsupports, all of these known materials possess only textural pores andlack the regular framework-confined porosity of a molecular sieve. Thepresent invention uses low cost, non-toxic and recyclablepolyethylene-based surfactants to prepare new mesoporous aluminamolecular sieves with properties of potential commercial importance topetroleum refining. Textural aluminas already enjoy an especiallyimportant role in Fluid Catalytic Cracking (FCC) (of petroleum)microsphere technology. One of the major functions of alumina is to trapmetal ion contaminants in the feed, particularly nickel. Alumina alsomediates the porosity of the microsphere and moderates theBronsted/Lewis acidity. These latter factors help control the lightgases and coke make of the cracking reactions and the catlaystdeactivation rate. Substantial improvements in FCC cracking performancecan be realized by adding new molecular sieve functionality to thealumina components. In addition to tailoring the pore structure andshape selectivity of these new molecular sieves, modifiers (e.g.zirconia and other metals) can be incorporated into the aluminas inorder to reduce the acidity under FCC, hydrotreating and mildhydrotreating conditions. The pore structure of these new sieves issufficiently large to support monolayers of MoS₂ for improvedhydrotreating applications. The alumina molecular sieves areparticularly useful for heavy residual cracking (i.e., the heavierfractions of petroleum not processable by conventional zeolite-basedcatalysts); mild hydrocracking of petroleum (low H₂ pressure); andhydrocracking (high H₂ pressure) of petroleum.

It is intended that the foregoing description be only illustrative ofthe present invention and that the present invention be limited only bythe hereinafter appended claims.

We claim:
 1. A synthetic, semi-crystalline inorganic oxide compositionhaving at least one resolved x-ray reflection corresponding to a latticespacing of 3 to 10 nm, framework confined channels between about 2 and10 nm diameter, and a specific surface area of 300 to 1400 square metersper gram and having a disordered assembly of worm channels.
 2. Asynthetic, semi-crystalline inorganic oxide composition prepared byreacting a mixture of a non-ionic poly(alkylene oxide) derivedsurfactant as a template (N°) and a neutral inorganic oxide precursor(I°), followed by hydrolysis and crosslinking of the inorganic oxideprecursor to provide the composition and having a disordered assembly ofworm channels.
 3. The composition of claim 2 wherein the template isremoved from the composition.
 4. The composition of claim 2 wherein thesurfactant has a terminal hydroxyl group.
 5. The composition of claim 2which has the formula:

    nR-EO/A.sub.x O.sub.y

wherein A_(X) O_(Y) is an anhydrous form of the composition, whereinR-EO is selected from the group consisting of nonionic alkylpolyethylene oxide, alkyl and aryl polyethylene oxide, and polyethyleneoxide-polypropylene oxide-polyethylene oxide block co-polymer molecules,A is a metal atom; O is oxygen and x and y are the molar stoichiometriesof A and O, such that in the composition when calcined, n is about 0, xis about 1 and y is between about 1 and
 3. 6. The composition of claim 2which has the formula:

    nR-EO/A.sub.v G.sub.w Si.sub.x D.sub.y O.sub.z

wherein A_(v) G_(w) Si_(x) D_(y) O_(z) is an anhydrous form of thecomposition, wherein R-EO is selected from the group consisting ofnonionic alkyl polyethylene oxide, alkyl and aryl polyethylene oxide andpolyethylene oxide-polypropylene oxide-polyethylene oxide blockco-polymer molecules wherein when R-EO is present n is between about0.01 and 1; A is at least one optional trivalent element selected fromthe group consisting of B, Cr, Al, Ga and Fe; G is at least one optionaltetravalent metallic element selected from the group consisting of Sn,Ge, Ti, V, Hf and Zr; Si is silicon; D is optional and is a pentavalentor hexavalent element selected from the group consisting of Sb, Cr, Nb,Ta, V, W and Mo; O is oxygen and v, w, x, y and z are the molarstoichiometries of A, G, Si, D and O respectively, wherein in thecomposition when calcined, n is about 0, 0≦v≦2, 0≦w≦1, 0≦x≦1,0.001≦y≦2and 1≦z≦3.
 7. The composition of claim 2 having X-raydiffraction patterns with at least one reflection corresponding to alattice spacing of between about 3 to 10 nm.
 8. The composition of anyone of claims 1 or 2 which after calcination, has an N₂, O₂ or Aradsorption-desorption isotherm that has a step at P/P_(O) equal tobetween 0.2 and 0.7.
 9. The composition of claim 8 wherein a ratio oftextural to framework-confined mesoporosity as determined by the N₂, O₂or Ar adsorption isotherm is less than or equal to about 0.2.
 10. Thecomposition of claim 2 wherein said composition has a specific surfacearea between 300 and 1400 m² per gram.
 11. The composition of claim 2wherein a molar ratio of nonionic surfactant to inorganic oxideprecursor in the reaction mixture is between 0.01 and 1.0.
 12. Thecomposition of claim 1 having an X-ray diffraction pattern selected fromthe group consisting of FIGS. 3 and
 5. 13. The compositions of claim 1having an N₂ adsorption-desorption isotherms and Horvath-Kawazoe poresize distribution selected from the group consisting of FIGS. 4A and 6A.14. The composition of claim 2 in which the template has been removed bycalcination.
 15. The composition of claim 2 in which the template hasbeen removed through solvent extraction.
 16. The composition of claim 1having an X-ray diffraction pattern as shown in FIG.
 7. 17. Thecomposition of claim 1 having N₂ adsorption-desorption isotherms andHorvath-Kawazoe pore size distribution as shown in FIG. 8A.
 18. Thecomposition of claim 6 in which the template has been removed bycalcination.
 19. The composition of claim 6 in which the template hasbeen removed through solvent extraction.
 20. The composition of any oneof claims 1 or 2 in which at least one transition metal is dispersed orimpregnated in the channels in the composition, selected from the groupconsisting of Rh, Nb, Re, Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd,Sn, Ti, V, W, Zn and Zr.
 21. The composition of any one of claims 1 or 2containing transition metal substituted organic macrocycles in thechannels.
 22. The composition of any one of claims 1 and 2 wherein thecomposition has surfaces functionalized by an alkyl metal alkoxide. 23.The composition of any one of claims 2 and 6 wherein upon removal of thetemplate the composition has surfaces that have been functionalized byreaction with metal carboxylate precursors, silylation reagents oralkylating reagents.
 24. The composition of any one of claims 1 or 2wherein surfaces of the compositions have been functionalized byreaction of the composition upon removal of the template and calcinationwith various reagents selected from the group consisting of metalnitrates, chlorides, fluorides, silylation reagents and alkylationreagents.
 25. The compositions of claim 2 wherein the template (N°) isselected from the group consisting of primary, secondary and tertiaryfatty alcohol poly(ethoxylates).
 26. The compositions of claim 2 whereinthe nonionic template (N°) is an alkyl phenol poly-(ethoxylates). 27.The compositions of claim 2 wherein the nonionic template (N°) is afatty acid ethoxylate.
 28. The compositions of claim 2 wherein thenonionic template (N°) is a poly(ethylene oxide-propylene oxide) blockco-polymer.
 29. The composition of claim 2 wherein the template (N°) isselected from the group consisting of primary and secondary fatty aminepoly(ethoxylate).
 30. The composition of claim 2 wherein the template(N°) is a fatty acid poly(ethylene oxide-propylene oxide) blockco-polymer.
 31. The composition of claim 2 wherein the template (N°) isselected from the group consisting of fatty acid alkanolamides andethoxylates.
 32. The composition of claim 1 wherein the template (N°) isselected from the group consisting of sorbitan esters and sorbitanethoxylates.
 33. The composition of claim 1 wherein the inorganic oxideis alumina.
 34. The composition of claim 1 wherein the template (N°) isa polyamine propoxylate ethoxylate.
 35. A method for the preparation ofa synthetic semi-crystalline inorganic oxide composition whichcomprises:(a) mixing (i) a neutral inorganic oxide precursor (I°)containing at least one element selected from the group consisting ofdi-, tri-, tetra-, penta- and hexavalent elements and mixture thereof;(ii) a non-ionic poly(alkylene oxide) surfactant (S°) as a template; and(iii) a hydrolyzing agent to form a gel containing the composition; (b)separating at least some of the hydrolyzing agent and the surfactantfrom the gel to form the composition; and (c) optionally calcining thecomposition wherein the composition has a disordered assembly of wormchannels.
 36. The method of claim 35 wherein the gel is prepared by arandom order of addition of the template and neutral inorganic oxideprecursor.
 37. A method for the preparation of a synthetic,semi-crystalline inorganic oxide composition which comprises:(a)preparing a solution of a neutral inorganic oxide precursor (I°),containing at least one element selected from the group consisting ofdi-, tri-, tetra-, penta- and hexavalent elements and mixtures thereofwith stirring and optionally aging the inorganic oxide precursor (I°)solution; (b) preparing a homogeneous solution of a nonionicpoly(alkylene oxide) surfactant (S°) as a template in a hydrolyzingagent, and optionally in a co-solvent, by stirring it at a temperaturebetween about minus 20° and plus 100° C.; (c) mixing of the solutions ofsteps (a) and (b) at a temperature between about minus 20° and plus 100°C. to form a gel which is aged for at least about 30 minutes to form thecomposition; (d) separating at least some of the hydrolyzing agent andsurfactant from the composition; and (e) optionally calcining thecomposition, wherein the composition has a disordered assembly of wormchannels.
 38. The method of claim 37 wherein the neutral precursor isselected from the group consisting of a metal alkoxide, an inorganiccomplex, a colloidal inorganic oxide solution, an inorganic oxide soland mixtures thereof.
 39. The method of claim 37 wherein said inorganicoxide precursor solution is mixed without aging.
 40. The method of claim37 wherein the template is separated from the composition and as anadditional step recycled after step (d).
 41. The method of claim 40wherein the template is separated by extraction with a solvent selectedfrom the group consisting of a neutral organic solvent, water andmixtures thereof.
 42. The method of claim 37 wherein in step (a) thestirring is at a temperature of at least minus 20° C. for at least 5minutes.
 43. The method of claim 37 wherein the composition is calcinedat about 300° to 1000° C. for at least about 30 minutes.
 44. The methodof claim 37 wherein the inorganic oxide is alumina.
 45. A method for thepreparation of a semi-crystalline inorganic oxide composition whichcomprises:(a) preparing a homogeneous solution of nonionic poly(ethyleneoxide) surfactant as a template (N°) in a lower alkyl alcohol solvent bymixing at ambient temperature; (b) adding an inorganic metal precursorto the solution of step (a) at ambient temperature under stirring for atleast 30 minutes to form a homogeneous solution; (c) slowly adding asolution of a hydrolyzing agent to the homogeneous solution to form agel as a first precipitate in the solution; (d) aging of the firstprecipitate with stirring; (e) redispersing the first precipitate in alower alkyl alcohol; (f) aging the redispersion under stirring atambient temperature for 16 to 48 hours to form a second precipitate; (g)separating the solution, lower alkanol and at least some of the templatefrom the second precipitate by washing once with ethanol; (h) drying thesecond precipitate in air at ambient temperature to form thecomposition; (i) optionally heat treating the composition to at least373° K in air for at least 16 hours; (j) optionally removing thetemplate form the composition by solvent extraction; and (k) optionallycalcining the composition at a temperature between about 673° K and 973°K in air for at least 4 hours to remove any remaining template and tocross-link the composition, wherein the composition has a disorderedassembly of worm channels.
 46. The method of claim 45 wherein thecalcining is by combustion in air.
 47. A method for the preparation ofsynthetic, semi-crystalline inorganic silicon dioxide composition whichcomprises:(a) preparing a homogeneous aqueous solution of a nonionicpoly(ethylene oxide) derived surfactant template (N°) with mixing atambient temperature; (b) adding an inorganic silica precursor to thesolution of step (a) at ambient temperature with stirring to form asolid, precipitate; (c) aging the precipitate with stirring at ambienttemperature for between 16 and 48 hours; (d) separating the aqueoussolution and template from the precipitate followed by washing once withdeionized water; (e) drying the precipitate in air at ambienttemperature; (f) heat treating the air dried precipitate in air at least373° K for at least 16 hours; (g) optionally removing any remainingtemplate by solvent extraction from the heat treated precipitate; and(h) calcining the precipitate at a temperature between 673° K and 973° Kin air for at least 4 hours to remove any remaining template andcross-link the composition, wherein the composition has a disorderedassembly of worm channels.
 48. The method of claim 47 wherein thecalcining is by combustion in air.
 49. In a method for cracking apetroleum product using a catalyst, the improvement which comprisesusing a catalyst which is a synthetic, semi-crystalline inorganic oxidecomposition having at least one resolved x-ray reflection correspondingto a lattice spacing of 3 to 10 nm, a framework wall thickness of atleast about 2 nm, framework confined pores between about 2 and 10 nm, anelementary particle size greater than 500 nm, and a specific surfacearea of 300 to 1400 square meters per gram and having a disorderedassembly of worm channels.
 50. The method of claim 49 wherein theinorganic oxide is alumina.